JPH09165518A - Polymer flameproofed with phosphate - Google Patents

Polymer flameproofed with phosphate

Info

Publication number
JPH09165518A
JPH09165518A JP8135621A JP13562196A JPH09165518A JP H09165518 A JPH09165518 A JP H09165518A JP 8135621 A JP8135621 A JP 8135621A JP 13562196 A JP13562196 A JP 13562196A JP H09165518 A JPH09165518 A JP H09165518A
Authority
JP
Japan
Prior art keywords
molecular weight
phosphate
composition
weight
thermoplastic resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP8135621A
Other languages
Japanese (ja)
Other versions
JP3961046B2 (en
Inventor
Qamar Singh Bhatia
カマール・シン・バーティア
Robert L Howe
ロバート・エル・ハウ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of JPH09165518A publication Critical patent/JPH09165518A/en
Application granted granted Critical
Publication of JP3961046B2 publication Critical patent/JP3961046B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant thermoplastic resin composition having excellent heat-deflection temperature and impact resistance and useful for various molded articles by mixing a moldable thermoplastic resin with a specific flame retardant
SOLUTION: (A) A moldable thermoplastic resin [e.g. aromatic polycarbonate, polyphenylene ether, polyalkylene terephthalate, polyether-imide (ester), polyamide or styrene-containing polymer, especially a mixture of a polyphenylene ether resin and a high-impact polystyrene] is mixed with (B) a flame retardant consisting of (B1) a low-molecular phosphate having a molecular weight of ≥500, especially 500-2,000 [e.g. a compound of formula (R1 to R4 are each an aryl or an alkaryl; X is an arylene; (m) is 0 or 1; (n) is 1-5)] and (B2) a high- molecular weight phosphate having a molecular weight of ≥2,300, especially 2,300-11,000 [e.g. a compound of formula ((n) is 6-35)]. The mixing weight ratio of B1:B2 is 10:90 to 90:10 and the ratios of the components A and B are 75-97wt.% and 25-3wt.%, respectively.
COPYRIGHT: (C)1997,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、成形用途向けの難燃性
ポリマー組成物であって、熱可塑性成形用樹脂と特定の
ホスフェート難燃剤とを混合して含むポリマー組成物に
関する。ホスフェート難燃剤は、２種のホスフェート、
即ち低分子量ホスフェートと高分子量ホスフェートとの
組み合わせ又は混合物を含む。また本発明は、本発明の
組成物を用いて成形される物品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polymer composition for molding use, which comprises a thermoplastic molding resin and a specific phosphate flame retardant in a mixture. Phosphate flame retardants are two types of phosphate,
That is, it includes a combination or mixture of low and high molecular weight phosphates. The invention also relates to articles molded using the compositions of the invention.

【０００２】[0002]

【従来の技術】従来の技術では、ポリマー又は熱可塑性
成形用樹脂のための難燃剤として、ホスフェート（リン
酸エステル）、具体的にはリン酸トリフェニル、リン酸
トリクレジル、リン酸ジフェニルクレジル等のモノホス
フェートを用いることが開示されている。これらのモノ
ホスフェートエステルは、熱可塑性組成物が射出成形等
の方法で成形された場合に、表面へ移行する傾向を有
し、いわゆる「滲出(juicing) 」を招く。滲出とは、成
形中に成形品の表面へ添加物が移行することである。ま
た、良好な難燃性を獲得するためには、しばしばその他
の難燃剤、具体的には含ハロゲン（ハロゲンを含有す
る）難燃剤をモノホスフェートエステルと併用する必要
がある。ハロゲン難燃剤は、環境上の観点から、及び成
形品の表面にピッチング（孔食）を生ずることから望ま
しくない。一方、特定のホスフェートエステルを高濃度
で用いると、耐熱性及び耐衝撃性の低下を招くことがあ
る。2. Description of the Related Art In the prior art, phosphate (phosphate ester), specifically, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, etc., is used as a flame retardant for polymers or thermoplastic molding resins. It is disclosed to use the monophosphate. These monophosphate esters have a tendency to migrate to the surface when the thermoplastic composition is molded by a method such as injection molding, which causes so-called "juicing". Exudation is the migration of additives to the surface of molded articles during molding. Further, in order to obtain good flame retardancy, it is often necessary to use other flame retardants, specifically, halogen-containing (halogen-containing) flame retardants in combination with the monophosphate ester. Halogen flame retardants are undesirable from an environmental point of view and because they cause pitting on the surface of molded articles. On the other hand, when a specific phosphate ester is used at a high concentration, heat resistance and impact resistance may be deteriorated.

【０００３】Gosen らの米国特許第５，２０４，３９４
号は、芳香族ポリカーボネートと、アクリロニトリル−
ブタジエン−スチレン（ＡＢＳ）のような含スチレン共
重合体と、オリゴマー状ホスフェート難燃剤との組成物
を開示している。この特許は更に、この組成物中に用い
られるオリゴマー状ホスフェートが種々の異なるオリゴ
マーの配合物でもよいことを開示している（第４欄、第
４６〜６６行）。US Pat. No. 5,204,394 to Gosen et al.
No. is aromatic polycarbonate and acrylonitrile-
Disclosed are compositions of styrene-containing copolymers such as butadiene-styrene (ABS) and oligomeric phosphate flame retardants. This patent further discloses that the oligomeric phosphate used in the composition may be a blend of various different oligomers (col. 4, lines 46-66).

【０００４】しかし、難燃剤として高分子量ホスフェー
トを用いること、換言すれば本発明で用いられている大
きさを有する高分子量を用いること、又は本発明で用い
ているように低分子量ホスフェートと高分子量ホスフェ
ートとの組み合わせを用いることを開示した従来技術の
実例は存在していない。したがって、本発明の目的は、
ハロゲン系難燃剤を用いずに、良好な難燃性を有する熱
可塑性成形用組成物を提供することにある。However, the use of high molecular weight phosphates as flame retardants, in other words the use of high molecular weights having the sizes used in the present invention, or low molecular weight phosphates and high molecular weights as used in the present invention. There are no prior art examples disclosing the use of combinations with phosphates. Therefore, the object of the present invention is to
It is intended to provide a thermoplastic molding composition having good flame retardancy without using a halogen-based flame retardant.

【０００５】本発明の更なる目的は、良好な加熱撓み温
度及び良好な耐衝撃性を有する難燃性組成物を提供する
ことにある。本発明のもう一つの目的は、本発明の組成
物から調製されており、加熱撓み性及び耐衝撃性という
機械的特性が良好である難燃性熱可塑性成形品を提供す
ることにある。A further object of the invention is to provide a flame retardant composition having good heat deflection temperature and good impact resistance. Another object of the present invention is to provide a flame-retardant thermoplastic molded article which is prepared from the composition of the present invention and has good mechanical properties such as heat deflection and impact resistance.

【０００６】本発明のこれらの目的及びその他の目的
は、本発明の以下の記載から明らかとなろう。These and other objects of the invention will be apparent from the following description of the invention.

【０００７】[0007]

【課題を解決するための手段】本発明の概要 本発明は、非ハロゲン系難燃剤を用いて、優れた難燃性
を有しながら加熱撓み温度、耐衝撃性及び流動性という
機械的特性を良好に保持する熱可塑性樹脂成形用組成物
を指向する。具体的には、本発明で用いられる難燃剤
は、低分子量ホスフェートと高分子量ホスフェートとの
組み合わせである。低分子量ホスフェートの分子量は、
少なくとも約５００、好適には約５００〜約２０００で
ある。高分子量ホスフェートの分子量は、少なくとも約
２３００、好適には約２３００〜約１１，０００であ
る。SUMMARY OF THE INVENTION The present invention uses a non-halogen flame retardant and provides mechanical properties such as heat deflection temperature, impact resistance and fluidity while having excellent flame retardancy. The present invention is directed to a thermoplastic resin molding composition that holds well. Specifically, the flame retardant used in the present invention is a combination of low and high molecular weight phosphates. The molecular weight of low molecular weight phosphate is
It is at least about 500, preferably about 500 to about 2000. The molecular weight of the high molecular weight phosphate is at least about 2300, preferably about 2300 to about 11,000.

【０００８】本発明の詳細 前述のように、本発明は、難燃性熱可塑性成形用組成物
及びこれから成形される物品を指向する。この難燃性熱
可塑性成形用組成物は、熱可塑性成形用樹脂と、難燃性
添加物とを混合して含んでおり、難燃性添加物は、低分
子量ホスフェートと高分子量ホスフェートとを組み合わ
せて含んでいる。本発明で用いられるホスフェートは、
好適には次式で表わされる。 Details of the Invention As mentioned above, the present invention is directed to flame retardant thermoplastic molding compositions and articles molded therefrom. This flame-retardant thermoplastic molding composition contains a thermoplastic molding resin and a flame-retardant additive in a mixed state, and the flame-retardant additive is a combination of a low molecular weight phosphate and a high molecular weight phosphate. Included. The phosphate used in the present invention is
It is preferably represented by the following equation.

【０００９】[0009]

【化２】 Embedded image

【００１０】式中、Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 は個別
に、アリール基又はアルカリール基の中から選択され、
Ｘはアリーレン基であり、ｍは０又は１の整数である。
低分子量ホスフェートの場合には、ホスフェートはオリ
ゴマー状ホスフェートであって、ｎは１〜５の整数であ
る。本発明の低分子量ホスフェートは、上式を有する又
は有さないによらず、その分子量は少なくとも約５０
０、好適には約５００〜約２０００であって、この場合
のｎは１〜５である。本発明の高分子量ホスフェート
は、上式を有する又は有さないによらず、その分子量は
少なくとも約２３００、好適には約２３００〜約１１，
０００であって、この場合のｎは約６〜３５の整数であ
る。更に好適には、本発明の高分子量ホスフェートの分
子量は、少なくとも約５０００であり、最適には少なく
とも約７５００である。低分子量ホスフェートの分子量
が高分子量ホスフェートの分子量と重複しないことが重
要である。Wherein R 1 , R 2 , R 3 and R 4 are individually selected from aryl or alkaryl groups,
X is an arylene group, and m is an integer of 0 or 1.
In the case of low molecular weight phosphate, the phosphate is an oligomeric phosphate and n is an integer from 1-5. The low molecular weight phosphates of the present invention, whether with or without the above formula, have a molecular weight of at least about 50.
0, preferably about 500 to about 2000, where n is 1-5. The high molecular weight phosphates of the present invention, whether with or without the above formula, have a molecular weight of at least about 2300, preferably about 2300 to about 11,
000, where n is an integer of about 6-35. More preferably, the high molecular weight phosphates of the present invention have a molecular weight of at least about 5000 and optimally at least about 7500. It is important that the molecular weight of the low molecular weight phosphate does not overlap with the molecular weight of the high molecular weight phosphate.

【００１１】上式において、アリール基は、アリールで
もよいし、又はアルキルで置換されたアリール基、即ち
アルカリール基でもよい。好適には、アリール基は個別
に、クレジル基、フェニル基、キシレニル基、プロピル
フェニル基及びブチルフェニル基から選択される。アリ
ーレン基は、ヒドロキシ基を２つもつ化合物から誘導さ
れ、好適には、レゾルシノール、ヒドロキノン及びビス
フェノールＡから誘導される。より具体的には、アリー
ル基（Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 ）はフェニルであり、
より具体的なアリーレン基はビスフェノールＡから誘導
される。低分子量ホスフェートの場合、更に好適な低分
子量ホスフェートは、ビスフェノールＡテトラフェニル
ジホスフェートであり、このときｎは１、ｍは１、Ｘは
ビスフェノールＡから誘導されそして各Ｒはフェニルで
あって、この更に好適な低分子量ホスフェートの分子量
は約６９３である。In the above formula, the aryl group may be aryl or an alkyl-substituted aryl group, that is, an alkaryl group. Suitably, the aryl groups are individually selected from cresyl, phenyl, xylenyl, propylphenyl and butylphenyl groups. The arylene group is derived from a compound having two hydroxy groups, preferably resorcinol, hydroquinone and bisphenol A. More specifically, the aryl group (R 1 , R 2 , R 3 and R 4 ) is phenyl,
A more specific arylene group is derived from bisphenol A. In the case of low molecular weight phosphates, a more preferred low molecular weight phosphate is bisphenol A tetraphenyl diphosphate, where n is 1, m is 1, X is derived from bisphenol A and each R is phenyl, A more suitable low molecular weight phosphate has a molecular weight of about 693.

【００１２】高分子量ホスフェートの場合、最適なのは
ビスフェノールＡフェニルポリホスフェートであり、そ
の分子量は約１０，０５６である。上式を有するこの最
適な高分子量ホスフェートにおいては、各Ｒはフェニル
基、ＸはビスフェノールＡから誘導され、ｍは１、及び
ｎは約３２である。本発明の実施にあたり、本発明で用
いられる熱可塑性樹脂は、射出成形、圧縮成形、トラン
スファー成形、押出吹込成形又は異形押出により成形さ
れ得る熱可塑性成形用樹脂ならばどれでもよい。好適な
熱可塑性成形用樹脂は、芳香族ポリカーボネート、耐衝
撃性ポリスチレン、アクリロニトリル−ブタジエン−ス
チレン（ＡＢＳ）樹脂のような含スチレン共重合体及び
含スチレングラフト共重合体、ポリフェニレンエーテル
樹脂、ポリブチレンテレフタレート、ポリエチレンテレ
フタレート及びポリプロピレンテレフタレートの各樹脂
のようなポリアルキレンテレフタレート樹脂、ポリエー
テルイミド樹脂、ポリエーテルイミドエステル樹脂、ポ
リアミド樹脂、ポリフェニレンスルフィド樹脂、ポリフ
ェニルスルホン、ポリイミド樹脂並びにこれらの混合物
である。最適な樹脂は、芳香族ポリカーボネート、芳香
族ポリカーボネートとＡＢＳとの配合物、ポリフェニレ
ンエーテルと耐衝撃性ポリスチレンとの配合物、及びポ
リエーテルイミドである。In the case of high molecular weight phosphates, the most suitable is bisphenol A phenyl polyphosphate, the molecular weight of which is about 10,056. In this optimized high molecular weight phosphate having the above formula, each R is derived from a phenyl group, X is derived from bisphenol A, m is 1 and n is about 32. In carrying out the present invention, the thermoplastic resin used in the present invention may be any thermoplastic molding resin that can be molded by injection molding, compression molding, transfer molding, extrusion blow molding or profile extrusion. Suitable thermoplastic molding resins include aromatic polycarbonates, high impact polystyrene, styrene-containing copolymers and styrene-containing graft copolymers such as acrylonitrile-butadiene-styrene (ABS) resins, polyphenylene ether resins, polybutylene terephthalate. Polyethylene terephthalate resins such as polyethylene terephthalate and polypropylene terephthalate resins, polyetherimide resins, polyetherimide ester resins, polyamide resins, polyphenylene sulfide resins, polyphenyl sulfones, polyimide resins and mixtures thereof. The resins of choice are aromatic polycarbonates, blends of aromatic polycarbonates and ABS, blends of polyphenylene ethers with high impact polystyrene, and polyetherimides.

【００１３】ホスフェートの使用量は、当該熱可塑性成
形用樹脂組成物を難燃性にしながら、加熱撓み温度、耐
衝撃性及び流動性という特性を良好に保つような量であ
り得る。好適には、本発明の組成物は、熱可塑性樹脂と
ホスフェート難燃剤との総合重量を基準として、ホスフ
ェート難燃剤を約３重量％〜約２５重量％、更に好適に
は約５重量％〜約２０重量％含有する。The amount of the phosphate used may be such that the thermoplastic molding resin composition is made flame-retardant while maintaining good properties such as heat deflection temperature, impact resistance and fluidity. Preferably, the composition of the present invention comprises from about 3 wt% to about 25 wt% phosphate flame retardant, more preferably from about 5 wt% to about 25 wt%, based on the combined weight of thermoplastic resin and phosphate flame retardant. Contains 20% by weight.

【００１４】本発明の難燃剤は、低分子量ホスフェート
と高分子量ホスフェートとの組み合わせである。この難
燃剤は、当該難燃剤の重量を基準として約１０重量％〜
約９０重量％の低分子量ホスフェートと、これに対応し
て９０重量％〜約１０重量％の高分子量ホスフェートと
から実質的に成る。好適には、ホスフェートの組み合わ
せは、約４０重量％〜約７０重量％の低分子量ホスフェ
ートと、これに対応して約６０重量％〜約３０重量％の
高分子量ホスフェートとから実質的に成る。加えて、本
発明の組成物と共にその他の添加物を併用することもで
きる。これらの添加物には、他の難燃性向上用添加物、
ガラス繊維等の強化用添加物、雲母、タルク、酸化物の
ようなその他の鉱物性添加物、また可塑剤、光安定剤、
熱安定剤、加工助剤、耐衝撃性改良剤、離型剤等があ
る。The flame retardant of the present invention is a combination of low and high molecular weight phosphates. This flame retardant is about 10% by weight based on the weight of the flame retardant.
It consists essentially of about 90% by weight of low molecular weight phosphate and correspondingly about 90% to about 10% by weight of high molecular weight phosphate. Suitably, the phosphate combination consists essentially of about 40% to about 70% by weight of low molecular weight phosphate and correspondingly about 60% to about 30% by weight of high molecular weight phosphate. In addition, other additives may be used in combination with the composition of the present invention. These additives include other additives for improving flame retardancy,
Reinforcing additives such as glass fibers, other mineral additives such as mica, talc, oxides, plasticizers, light stabilizers,
There are heat stabilizers, processing aids, impact resistance improvers, release agents and the like.

【００１５】本発明の組成物から、使用した熱可塑性樹
脂及びその成形品の用途に応じて、優れた諸特性を併有
する成形品が製造される。好適には、本発明の組成物か
ら成形された物品では、ノッチ付きアイゾット衝撃強さ
は、ＡＳＴＭ Ｄ２５６に従って測定すると少なくとも
約５．０ｆｔ・ｌｂｓ／ｉｎ、荷重下での加熱撓み温度
は、ＡＳＴＭ Ｄ６４８に従って測定すると少なくとも
約２００°Ｆ、流動性は、厚み１／８インチのチャネル
でスパイラルフロー試験法によって測定すると少なくと
も約１８インチ、及び易燃性等級は、Underwriters Lab
oratory Bulletin ＵＬ９４に従って測定すると少なく
ともＶ１である。本発明の難燃剤を用いたＡＢＳ射出成
形用樹脂の場合には、射出成形された物品において、好
適には、ノッチ付きアイゾット衝撃強さは少なくとも約
７．０ｆｔ・ｌｂｓ／ｉｎ、荷重下での加熱撓み温度は
少なくとも約２００°Ｆ、流動性は少なくとも約２５．
０インチ、及びＵＬ９４等級は少なくともＶ１であり得
る。本発明の難燃剤を用いたポリフェニレンエーテル樹
脂系の場合、射出成形された物品において、好適には、
加熱撓み温度は少なくとも約２００°Ｆ、流動性は少な
くとも約１５インチ、及びＵＬ９４等級は少なくともＶ
１であり得る。From the composition of the present invention, a molded article having excellent properties can be produced depending on the thermoplastic resin used and the use of the molded article. Preferably, for articles molded from the compositions of the present invention, the notched Izod impact strength is at least about 5.0 ft.lbs / in as measured according to ASTM D256, and the heat deflection temperature under load is ASTM D648. According to the Underwriters Lab, the flowability is at least about 200 ° F, the flowability is at least about 18 inches as measured by the spiral flow test method in a channel with a thickness of 1/8 inch, and the flammability rating is Underwriters Lab.
At least V1 as measured according to oratory Bulletin UL94. In the case of ABS injection molding resins using the flame retardants of the present invention, the injection molded article preferably has a notched Izod impact strength of at least about 7.0 ft.lbs / in, under load. The heat deflection temperature is at least about 200 ° F. and the flowability is at least about 25.
0 inch, and UL94 rating may be at least V1. In the case of a polyphenylene ether resin system using the flame retardant of the present invention, in an injection molded article, preferably,
Heat deflection temperature of at least about 200 ° F, flowability of at least about 15 inches, and UL94 rating of at least V
It can be 1.

【００１６】[0016]

【実施例】本発明の様々な具体例を説明するために、以
下に実施例を掲げる。これらの実施例は、説明の目的に
限られており、本発明に対して所載の特定の物質又は特
定の条件のどのような限定も与えないものとする。実施例１ 本実施例で構成成分として用いた材料は、以下のとおり
である。 ＰＣ…ビスフェノールＡと塩化カルボニル（ホスゲン）
とから誘導された芳香族ポリカーボネート。重量平均分
子量は約２２，０００、塩化メチレン中で２５℃で測定
した固有粘度（Ｉ．Ｖ．）は約０．４０ｄＬ／ｇ。 ＨＲＧ…スチレン−アクリロニトリルをブタジエンゴム
に５０／５０の比でグラフトして調製した高ゴム含量グ
ラフト共重合体。 ホスフェート１…レゾルシノールを基本成分として有す
る種々のオリゴマー状ジホスフェートの混合物。 ホスフェート２…分子量が約６９３のビスフェノールＡ
テトラフェニルジホスフェート。 ホスフェート３…分子量が約１０，０５６のビスフェノ
ールＡフェニルポリホスフェート。 ＰＴＦＥ…ポリテトラフルオロエチレン 表１に記載した組成の各成分を、３０ｍｍの Werner Pf
leider二軸押出し機内で溶融温度を約５５０°Ｆ〜５６
０°Ｆとして配合し、押し出した。押出し物をペレット
化し、次いでこのペレットを約１９０°Ｆで約３時間に
わたって乾燥させた。そしてペレットを成形し、以下の
表１に記載した具体的な特性を測定するために用いられ
るＡＳＴＭ試験手順に従った標準試験標本とした。耐衝
撃性は、ノッチ付きアイゾット衝撃試験手順ＡＳＴＭ
Ｄ２５６によって、厚み約１／８インチの成形標本に関
して測定された。荷重（２６４ｐｓｉ）下での加熱撓み
温度（ＨＤＴ）は、１／４インチの成形された試験棒に
関して、ＡＳＴＭ試験手順Ｄ６４８に従って測定され
た。スパイラルフロー試験は、厚み１／８インチのチャ
ネル内で、溶融温度を約４８０°Ｆ及び成形温度を約１
５０°Ｆとして行われた。流動の長さが長いほど、標本
の流動性は良好であり、より加工しやすい。易燃性は、
厚み１／１６インチの試験標本に関して、Underwriters
Laboratory Bulletin ＵＬ９４の易燃性等級Ｖ０、Ｖ
１及びＶ２に従って測定された。EXAMPLES Examples are provided below to illustrate various embodiments of the present invention. These examples are for purposes of illustration only and are not intended to impose on the invention any limitation of the specific materials or specific conditions listed. Example 1 Materials used as constituent components in this example are as follows. PC: Bisphenol A and carbonyl chloride (phosgene)
An aromatic polycarbonate derived from. The weight average molecular weight is about 22,000, and the intrinsic viscosity (IV) measured at 25 ° C. in methylene chloride is about 0.40 dL / g. HRG ... A high rubber content graft copolymer prepared by grafting styrene-acrylonitrile onto butadiene rubber at a ratio of 50/50. Phosphate 1 ... A mixture of various oligomeric diphosphates having resorcinol as a basic component. Phosphate 2 ... Bisphenol A with a molecular weight of about 693
Tetraphenyl diphosphate. Phosphate 3 ... Bisphenol A phenyl polyphosphate having a molecular weight of about 10,056. PTFE ... Polytetrafluoroethylene Each component of the composition shown in Table 1 was mixed with 30 mm Werner Pf.
Melting temperature in leider twin screw extruder is about 550 ° F-56
Formulated as 0 ° F and extruded. The extrudate was pelletized and the pellets were then dried at about 190 ° F for about 3 hours. The pellets were then molded into standard test specimens according to the ASTM test procedure used to measure specific properties listed in Table 1 below. Impact resistance is notched Izod impact test procedure ASTM
Measured by D256 on molded specimens about 1/8 inch thick. Heat Deflection Temperature (HDT) under load (264 psi) was measured according to ASTM test procedure D648 for 1/4 inch molded test bars. The spiral flow test shows a melt temperature of about 480 ° F. and a molding temperature of about 1 in a 1/8 inch thick channel.
Performed as 50 ° F. The longer the flow length, the better the flowability of the specimen and the easier it is to process. Flammability is
Underwriters on 1/16 inch thick test specimens
Laboratory Bulletin UL94 flammability rating V0, V
1 and V2.

【００１７】試験結果を以下の表１に掲げる。 表 １ 配 合 １ ２ ３ ４ ＨＲＧ 81.05 80.05 80.05 80.05 ホスフェート１ 11 ホスフェート２ 10 6 ホスフェート３ 11 5 ＰＴＦＥ .2 .2 .2 .2 添加物 .95 .95 .95 .95 特 性 ノッチ付きアイゾット 9.0 7.1 8.6 2.3 (ft・lb/in) ＨＤＴ（°Ｆ） 204 236 214 188 フローチャネル（インチ） 28 25.5 29.75 32.5 ＵＬ９４（１／１６インチ） Ｖ０ Ｖ２ Ｖ０ Ｖ０ 添加物…ヒンダードフェノール、ホスファイト及び滑剤を含む安定剤パッケージ 。The test results are listed in Table 1 below. Table 1 Combination 1 2 3 4 HRG 81.05 80.05 80.05 80.05 Phosphate 1 11 Phosphate 2 10 6 Phosphate 3 11 5 PTFE .2 .2 .2 .2 2 Additive .95 .95 .95 .95 Specific notched Izod 9.0 7.1 8.6 2.3 (ft · lb / in) HDT (° F) 204 236 214 188 Flow channel (inch) 28 25.5 29.75 32.5 UL94 (1/16 inch) V0 V2 V0 V0 Additives ... Hindered phenol, phosphite and lubricant Stabilizer package including.

【００１８】実施例２ 実施例１を繰り返したが、本実施例で用いた組成は以下
の表２に記載したとおりである点が異なる。用いたポリ
フェニレンエーテルは、Ｉ．Ｖ．が約０．４６ｄＬ／ｇ
であって、ゼネラル・エレクトリック・カンパニィ製で
あった。耐衝撃性ポリスチレン（ＨＰＳ）は、ニューヨ
ーク州 Selkirk所在の GE-Huntsman Co.製であって、重
量平均分子量は約２００，０００、ゴム含有量は耐衝撃
性ポリスチレンの重量を基準として約１０．５重量％で
あった。得られた特性は、表１で用いたものと同じ試験
手順を用いて測定された。結果を以下の表２に掲げる。 Example 2 Example 1 was repeated with the difference that the composition used in this example was as set forth in Table 2 below. The polyphenylene ether used was I.I. V. Is about 0.46 dL / g
And it was made by General Electric Company. The high impact polystyrene (HPS) is manufactured by GE-Huntsman Co. of Selkirk, NY and has a weight average molecular weight of about 200,000 and a rubber content of about 10.5 based on the weight of the high impact polystyrene. % By weight. The properties obtained were measured using the same test procedure used in Table 1. The results are listed in Table 2 below.

【００１９】 ＰＳ…ポリスチレン 耐衝撃性改良剤…Shell Chemical Co.製のスチレン−ブ
タジエンブロック共重合体、Ｋｒａｔｏｎ Ｇ１６５
０。 添加物…ホスファイト、酸化物及びスルフィドを含む安
定剤パッケージ。 ポリエチレン…離型剤 これらの実施例からわかるように、低分子量ホスフェー
ト及び高分子量ホスフェートを用いると、良好な耐衝撃
性、荷重下での高い加熱撓み温度、加工を容易にする良
好な流動性及び優れた耐燃性という結果が生じた。この
ことは、表１の配合物３をその他の配合物と比較すると
わかる。注意していただきたい点は、配合物１は低分子
量ビスフェノールＡテトラフェニルジホスフェート（オ
リゴマー状ジホスフェート）を用い、配合物２は高分子
量ビスフェノールＡフェニルポリホスフェートを用い、
配合物４はオリゴマー状ジホスフェートの混合物を用い
ていることである。予期せぬ上述の結果から、本発明の
組成物（配合物３）が、対照配合物１、２及び４よりも
全般に良好な特性を有していることがわかった。表２で
は、ポリフェニレンエーテル組成物を用いた場合にも同
等の結果が得られている。荷重（２６４ｐｓｉ）下での
加熱撓み温度は、本発明の組成物、即ち表２の配合物２
において非常に良好である。また、難燃剤の移行（滲
出）も本発明の組成物では著しく減少した。[0019] PS: polystyrene Impact modifier: styrene-butadiene block copolymer from Shell Chemical Co., Kraton G165
0. Additives ... Stabilizer package containing phosphite, oxides and sulfides. Polyethylene-Release Agent As can be seen from these examples, low molecular weight phosphates and high molecular weight phosphates provide good impact resistance, high heat deflection temperature under load, good flowability to facilitate processing and The result was excellent flame resistance. This can be seen by comparing formulation 3 in Table 1 with the other formulations. Please note that formulation 1 uses low molecular weight bisphenol A tetraphenyl diphosphate (oligomeric diphosphate), formulation 2 uses high molecular weight bisphenol A phenyl polyphosphate,
Formulation 4 is to use a mixture of oligomeric diphosphates. The unexpected above results indicate that the composition of the invention (formulation 3) has generally better properties than the control formulations 1, 2 and 4. In Table 2, similar results are obtained when the polyphenylene ether composition is used. The heat deflection temperature under load (264 psi) was determined by the composition of the invention, namely formulation 2 in Table 2.
Is very good at. Also, the migration (leaching) of flame retardant was significantly reduced with the composition of the present invention.

【００２０】これらの実施例で用いたポリマーに加え
て、本明細書で開示したその他のポリマーも、実施例１
及び実施例２のポリマーで得られたものと同等の結果を
生むであろう。上述の開示内容を鑑みて当業者には本発
明の様々な変形が示唆されようが、このような変形はす
べて、本発明に付した特許請求の範囲内に含まれるもの
とする。In addition to the polymers used in these examples, other polymers disclosed herein were also tested in Example 1.
And will give results comparable to those obtained with the polymer of Example 2. Various modifications of the invention will suggest themselves to those skilled in the art in light of the above disclosure, but all such modifications are intended to be included within the scope of the claims appended to the invention.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 71/12 ＬＱＭ Ｃ０８Ｌ 71/12 ＬＱＭ 77/00 ＫＬＢ 77/00 ＫＬＢ 79/08 ＬＲＢ 79/08 ＬＲＢ (72)発明者 ロバート・エル・ハウ アメリカ合衆国、ニューヨーク州、グリー ンビル、アールアール・１・ボックス・ 433（番地なし)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI Technical display location C08L 71/12 LQM C08L 71/12 LQM 77/00 KLB 77/00 KLB 79/08 LRB 79/08 LRB (72) Inventor Robert El Howe ar 1 box 433 (no street number), Greenville, NY, USA

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 成形可能な熱可塑性樹脂と、当該組成物
を難燃性にする上で充分な量の難燃剤とを混合して含ん
でおり、該難燃剤が分子量が少なくとも約５００である
低分子量ホスフェートと分子量が少なくとも約２３００
である高分子量ホスフェートとの組み合わせから実質的
に成る（但し両者の分子量は重複しない）、成形可能な
難燃性熱可塑性樹脂組成物。1. A mixture of a moldable thermoplastic resin and a flame retardant in an amount sufficient to render the composition flame retardant, the flame retardant having a molecular weight of at least about 500. Low molecular weight phosphate and a molecular weight of at least about 2300
A moldable flame-retardant thermoplastic resin composition consisting essentially of a combination with a high-molecular-weight phosphate which is (but the molecular weights of the two do not overlap). 【請求項２】 前記低分子量ホスフェートの分子量が約
５００〜約２０００である請求項１の組成物。2. The composition of claim 1 wherein the low molecular weight phosphate has a molecular weight of about 500 to about 2000. 【請求項３】 前記高分子量ホスフェートの分子量が約
２３００〜約１１，０００である請求項１の組成物。3. The composition of claim 1, wherein the high molecular weight phosphate has a molecular weight of about 2300 to about 11,000. 【請求項４】 前記難燃剤が、当該ホスフェート難燃剤
の総合重量を基準として約１０重量％〜９０重量％の低
分子量ホスフェートと、これに対応して約９０重量％〜
１０重量％の高分子量ホスフェートとから実質的に成る
請求項１の組成物。4. The flame retardant comprises from about 10% to 90% by weight of low molecular weight phosphate, based on the total weight of the phosphate flame retardant, and correspondingly from about 90% by weight.
The composition of claim 1 consisting essentially of 10% by weight of high molecular weight phosphate. 【請求項５】 前記熱可塑性樹脂が、芳香族ポリカーボ
ネート、ポリフェニレンエーテル、ポリアルキレンテレ
フタレート、ポリエーテルイミド、ポリエーテルイミド
エステル、ポリアミド、含スチレンポリマー及びこれら
の配合物の中から選択される請求項１の組成物。5. The thermoplastic resin is selected from aromatic polycarbonates, polyphenylene ethers, polyalkylene terephthalates, polyetherimides, polyetherimide esters, polyamides, styrene-containing polymers and blends thereof. Composition. 【請求項６】 前記熱可塑性樹脂が芳香族ポリカーボネ
ートと含スチレンポリマーとの混合物である請求項５の
組成物。6. The composition according to claim 5, wherein the thermoplastic resin is a mixture of an aromatic polycarbonate and a styrene-containing polymer. 【請求項７】 前記熱可塑性樹脂がポリフェニレンエー
テル樹脂と耐衝撃性ポリスチレンとの混合物である請求
項５の組成物。7. The composition of claim 5 wherein said thermoplastic resin is a mixture of polyphenylene ether resin and high impact polystyrene. 【請求項８】 約７５重量％〜約９７重量％の前記熱可
塑性樹脂と、これに対応して約２５重量％〜約３重量％
の前記難燃剤とから実質的に成る請求項１の組成物。8. About 75% to about 97% by weight of said thermoplastic resin and correspondingly about 25% to about 3% by weight.
The composition of claim 1 consisting essentially of: the flame retardant. 【請求項９】 前記低分子量ホスフェートが次式を有し
ており、 【化１】 式中、Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 は個別に、アリール基
又はアルカリール基の中から選択され、Ｘはアリーレン
基であり、ｍは０〜１の整数であり、ｎは１〜５の整数
であり、Ｐはリンである請求項１の組成物。9. The low molecular weight phosphate has the formula: In the formula, R 1 , R 2 , R 3 and R 4 are individually selected from an aryl group or an alkaryl group, X is an arylene group, m is an integer of 0 to 1, and n is 1 The composition of claim 1 which is an integer from -5 and P is phosphorus. 【請求項１０】 前記高分子量ホスフェートが同じ前記
式を有しており、ｎは６〜３５の整数である請求項９の
組成物。10. The composition of claim 9, wherein the high molecular weight phosphates have the same formula and n is an integer from 6 to 35.
JP13562196A 1995-06-07 1996-05-30 Phosphate flame retardant polymer Expired - Fee Related JP3961046B2 (en)

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US08/472799 1995-06-07

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KR100448419B1 (en) * 1997-12-04 2004-11-16 삼성종합화학주식회사 Mono(2,2,6,6-tetramethyl piperidyl) diaryl phosphate compounds having improved fire retardancy and thermal resistance and low tarnishing, preparation method thereof, and resin composition comprising the same
JP2001294746A (en) * 2000-04-12 2001-10-23 Sumitomo Chem Co Ltd Polyphenylene ether-based resin composition
JP2008531977A (en) * 2005-03-07 2008-08-14 ソルヴェイ アドバンスド ポリマーズ リミテッド ライアビリティ カンパニー Ammunition case
WO2014025107A1 (en) * 2012-08-06 2014-02-13 제일모직 주식회사 Branched polycarbonate resin, and method for preparing same

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TW360681B (en) 1999-06-11
CN1148064A (en) 1997-04-23
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EP0747424A1 (en) 1996-12-11
KR100445084B1 (en) 2004-10-20
ES2149428T3 (en) 2000-11-01
US6815476B1 (en) 2004-11-09
JP3961046B2 (en) 2007-08-15
EP0747424B1 (en) 2000-08-30
CN1140588C (en) 2004-03-03
DE69610020D1 (en) 2000-10-05
KR970001435A (en) 1997-01-24

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